In the field of photographic processing service in recent years, silver halide color photographic light-sensitive materials of high image quality, which can be easily (simply) and rapidly processed, are desired for improved service for the user, or as a means of improving productivity. At present, a light-sensitive material containing a high-silver chloride emulsion, which material can be processed for a color development time of 45 seconds, with a total processing time of 4 minutes or less, is usually employed. However, the silver halide color photographic light-sensitive material is not satisfactory with respect to ease and processing speed compared with other color systems (e.g. an electrostatic transfer system, a thermal transfer system, and an ink jet system), and there is a demand for further enhancement of processing easiness and speed.
Stabilization of the photographic properties of a silver halide color photographic light-sensitive material after processing is always desired. In particular, there is a need for improved fluctuation in fog and sensitivity under varying conditions during storage of a light-sensitive material in an unexposed state. Particularly with fluctuation in fog, the white background is greatly affected, to significantly deteriorate image quality.
As techniques to improve the white background, there are techniques to improve the washing of sensitizing dyes and irradiation-preventing dyestuffs, to improve it by using a fluorescent brightening agent, and to improve the packing density of a white pigment in a support (base), in addition to reducing fog of the silver halide emulsion. For example, attempts to improve an absolute value of whiteness by using a specific support are described in JP-A-10-333277 (“JP-A” means unexamined published Japanese patent application), JP-A-11-52513, JP-A-11-65024, JP-A-6-250331, JP-A-6-167772 and JP-A-6-167775. However, the techniques described above do not reach drastic or radical improvements, and further improvements have been desired.
On the other hand, a paper support laminated with polyethylene has been usually used as a support for color paper. The polyethylene-laminated paper support is a technique that is useful in reducing the burden of washing and drying, and in imparting rapid processability, by improving the water resistance of the support and preventing a processing solution from penetrating into the paper. Further, the polyethylene-laminated paper support is also advantageous, in that the whiteness of the light-sensitive material can be improved by dispersing and containing a white pigment, such as titanium oxide, in polyethylene.
However, if it is attempted to further improve whiteness and sharpness, there is a limit to the density of titanium oxide dispersed in polyethylene, and thus the polyethylene-laminated paper support is not necessarily satisfactory.
On the other hand, if a polyester-series resin is used as a laminate material, the resulting support is far advantageous in the respect that smoothness is high, while a white pigment can be dispersed in high light packing, whereas there are difficulties in production, such as the burden of high costs and insufficient adhesion of the coated material. Thus further improvement and new support techniques have been desired.
As a result of various eager studies, the present inventors have found that a support, whose whiteness is improved by dispersing titanium oxide or/and forming pores, in a biaxially oriented polyolefin resin, is used in combination with a pyrazolotriazole-type magenta coupler represented by the following formula (I): wherein, in formula (I), R1a and R1b each independently represent a hydrogen atom or a substituent, and X1a represents a hydrogen atom or a group that can be split-off by reaction with an oxidized product of a color-developing agent, thereby a silver halide color photographic light-sensitive material having high sensitivity and improved significantly in sharpness, whiteness, curling properties, and color reproduction, can be prepared.
However, when the above support and the pyrazolotriazole-type magenta coupler with a relatively low pKa value, represented by formula (I), were used, it was found that there are the problems that the sensitivity of the magenta-color-forming layer is changed with the lapse of time during long-term storage of the light-sensitive material, and that the gradation in the shoulder part is soft-toned. In particular, the sensitivity of the roll-processed light-sensitive material is significantly changed during long-term storage, and further improvements have been desired.
In recent years, various color imaging means different from the silver halide color photographic system, such as the ink jet system, the thermal transfer system, and the electron photographic system, have been developed and proposed. Compared with these methods, the silver halide color photographic system is excellent in image quality and costs. However, these systems have been rapidly developed in recent years, and the image quality in these systems has approached those in the silver halide color photographic system.
Further, the range of utilization of image to be printed is enlarged due to development of the technique of forming artificial images by computer (computer graphics).
Accordingly, even in the silver halide color photographic system, there is a demand for further improvements to realize higher image quality, while maintaining its superiority in costs.
For attaining higher image quality in silver halide color photographic light-sensitive materials, many techniques have been developed from various viewpoints. For example, mention can be made of the technique of gradation design, as described in JP-A-3-68938, as well as the techniques of improving whiteness by use of a resin coated paper in place of a baryta paper, or by use of a coupler excellent in color reproduction, as described in JP-A-5-150418, and by use of a support containing a fluorescent brightening agent, as described in U.S. Pat. No. 4,794,071.
In addition to these techniques, recently, a method of comprehensively improving image quality by computer processing of information on an image upon printing, onto a print material, of the image recorded on a material for photographing, is put to practical use (for example, Digital Mini-Lab System Frontier, trade name, manufactured by Fuji Photo Film Co., Ltd.). In this method, the printing of an image onto the print material is conducted not by a conventional method of exposing the print material to a light passing through a developed film having a negative image recorded thereon, but by a method of exposing the information on an image to a light in a scanning exposure system using a combination of a DMD (digital mirror device), a polygon mirror, or the like, with a light source, such as a laser or LED.
In such an exposure system, a shorter exposure time per picture element is advantageous to reduce the exposure time for the image as a whole, from the viewpoint of improvement on processing operation efficiency. At present, the exposure time per picture element in an exposure device in the scanning exposure system utilized in practice, is substantially 10−4 seconds or so, which is extremely short compared with the exposure time (about 1/10 second) in the conventionally used exposure device.
To keep up with such a short-time exposure, print materials for scanning exposure are also commercially available. To maximally demonstrate the superiority in costs and the convenience in the silver halide color photographic system, however, there is a need for print materials to which both the scanning exposure system and the conventional system can be applied; that is, print materials that are applicable to a wide range of exposure time. Some of such print materials are commercially available (e.g. Fuji G Color Film Super FA-FC/FA-FT, trade name, manufactured by Fuji Photo Film Co., Ltd.).
In spite of many such efforts to improve image quality, the current silver halide color photographic light-sensitive materials cannot satisfactorily keep up with the change in the exposure system. By way of example, there is the case where such materials are not satisfactory with respect to the expression of metallic texture (feeling) or the expression of images whose density is greatly changed in fine regions, as observed in a vivid space figure frequently used in computer graphics. In particular, this problem was significant in images formed in the scanning exposure system.
Color photography makes use of a method of obtaining a dye image, through development processing of a light-sensitive material having a dye-forming coupler and a silver halide emulsion on a support, with an aromatic primary amine color-developing agent, and the sequential reaction of a resultant oxidized product of the developing agent with the dye-forming coupler. To enhance this color-development processing more easily and rapidly is required very strongly in the industry of color photography, and a very large number of improvements have been added thereto, and new and faster systems have been developed every few years.
For processing speed enhancement, it is necessary to think about reducing the time in the respective steps of color development, bleach-fixing, washing, and drying. As a method for enhancement of processing speed, for example, International Published Patent WO87-04534 discloses a method of rapid processing with a color photographic light-sensitive material using a high-silver-chloride silver halide, as a photographic emulsion, and it is described therein that use of the high-silver-chloride emulsion is preferable from the viewpoint of rapid processing. By these efforts, a method of printing, onto a silver halide color printing paper for a high-silver-chloride print, of an image taken on a color negative film, is widespread as a method of rapidly and easily obtaining a high-quality image.
Further, in recent years, prints of various sizes, such as panorama size, high-vision size, or the like, can be easily obtained, according to the diversification of user needs. In such prints, there is a demand not only for size but also for smoothness and gloss for the texture of the print material, and supports meeting this demand are under development.
For example, European Patent EP-0507,489 discloses that a support for print superior to generally used polyolefins in smoothness and gloss on the surface thereof, can be obtained by use of a polyester as a water-resistant resin.
The present inventors studied silver halide color photographic light-sensitive materials superior in surface smoothness and gloss, particularly color photographic printing paper. As a result, a support for print superior to generally used polyolefins in smoothness and gloss on the surface thereof, can be certainly obtained by use of a polyester as a water-resistant resin. In this case, however, the following disadvantages were revealed: that desensitization occurs at pressurized or bent sites of the light-sensitive material, and further that fog is occurred on the light-sensitive material upon pressurization, particularly upon occurrence of abrasion marks.
Against this problem, JP-A-6-167771 discloses that the problem of easy occurrence of desensitization of a light-sensitive material using a polyester as the support, upon pressurization of the light-sensitive material during long-term storage, can be reduced by adding a silver halide emulsion sensitized with selenium, tellurium, or gold, to the light-sensitive emulsion layer. However, as a result of further extensive study, the present inventors found that pressure desensitization occurring upon pressurization of the light-sensitive material is further worsened by a combination of the silver halide emulsion and a blue-sensitizing dye, and further by making the layer thinner for rapid processing. Accordingly, further improvements have been desired.
On the other hand, against the above-mentioned problem, JP-A-6-289532 discloses that fog occurring at pressurized or bent sites of the light-sensitive material using a polyester as its support, can be reduced by defining a specific content of calcium in the light-sensitive material. However, the light-sensitive material is actually hardly bent by excessive force in the step of photographic printing, and there are many cases where a high-quality image cannot be realized due to fogging upon occurrence of abrasion marks during transportation or handling, without knowing such marks. In this respect, the disclosure neither fully solves the problem nor is practically usable.
Accordingly, it has been desired to develop a technique to reduce abrasion fog, without deterioration of surface gloss and smoothness.
For the silver halide color photographic light-sensitive material, a method of color-development processing, with a color-developing agent, of an exposed light-sensitive material containing three kinds of yellow, magenta, and cyan photographic couplers in three kinds of light-sensitive emulsion layers different in color sensitivity from each other on a support, is widely known. As the support, a white opaque support is used, and so-called RC raw paper, having polyolefin laminated on the paper, has been used particularly as a support for color paper.
In the case of this color paper, a print photograph with glossy texture is preferred by the general user in recent years, but if the glossiness by light reflection is too strong, it may be difficult to observe the print surface.
On the other hand, in the case of printing at the request of a user who dislike glossiness or desires printing with immensity (massive proportion), a color paper using so-called framed RC raw paper, such as a matte surface, silk surface, or the like, having a previously-surface-treated RC raw paper, is subjected to printing. However, the print on the color paper using the framed RC raw paper exhibits too strong light reflection depending on the position of the light source for observation, and it cannot be said that an immensity and satisfactory image pattern (design) can be perfectly obtained.
In addition, methods of improving surface glossiness by achieving a matte effect, through fine grains contained in the surface or the inside of a light-sensitive material, are disclosed, for example, in JP-A-61-147248, JP-A-1-142630, JP-A-6-75331, and JP-A-7-261342, and the print obtained by these methods can provide a design with some degrees of immensity, but there is the disadvantage that the processed print is easily damaged during conveyance and transportation, or it is easily curled (warped) when the print is left at low humidity.
Accordingly, a method of using both a predetermined or greater amount of porous fine grains and latex in the light-sensitive material, thereby lessening damage on the print and preventing curling under low humidity, is disclosed in JP-A-10-104794, but it cannot be said that prevention of curling when the print is left in high humidity is satisfactory.
Conventionally, toughness of image-displaying elements including silver halide photographic light-sensitive materials, has been pursued. The image-displaying element is a material displaying an image, including drawings, letters, figures, or the like, in addition to photographs, on a support comprising a paper and/or plastic. Up to now, development has been made mainly from the viewpoint of image storability in pursuing toughness, and in recent years, the viewpoint of toughness against physical destruction, such as deformation, bending, or cracking, has become important. This is because, as a result of the technical developments made hitherto, in particular related to silver halide photographic light-sensitive material, images can be stored and appreciated for dozens of years under usual storage conditions, and thus a materials resistance to physical deformation or destruction, upon attachment to a wall via pushpins or an adhesive tape, and upon bending due to wind or repeated attachment, has become important.
As a result of study aimed at preventing physical deformation or destruction, the present inventors found that, when a resin which is composed of a polyester as a main component described, for example, in JP-A-6-167775, is coated on a raw paper, thereby increasing the rigidity of the resultant support, this support can exhibit physical strength as high as several times that of a conventional photographic print of a paper support coated with polyethylene. Meanwhile, it was also found that the same effect can be achieved in a method of obtaining a photographic print having resistance to cracking due to deformation or bending, as disclosed in British Patent GB-2325750.
However, it was found that, when a photographic print using a support having physical strength increased by these methods, is subjected to continuous printing, using an automatic developing machine and/or an automatic cutting machine, the corners of the print, which should usually be right-angled, are not right-angled and tend to have shapes with sharp burrs, after several thousand sheets are printed. If these burrs are present, when several hundred sheets of photographic print are tried to stack flat to pile them up, they easily collapse without being piled up vertically. Accordingly, such the photographic prints are not preferable, since they are inferior in stacking (piling-up) property, thus disadvantageously increasing the burden in working in laboratories.